Polymers of unsaturated derivatives of 3-sulfolanol



. epic UNITED STAT PQLYMERS F UNSATURATED BERNA- TIVES 0F 3-SULFOLANOL Edward C. Shokal, Oakland, and Rupert C. Morris,

Berkeley, Calif., assignors to Shell Development Company, San Francisco, Calii, a corpo= ration of'Delaware No Drawing. Application August 19, 1943, Serial No. 499,286

' 6 Claims. (Cl. 260-79) 1 2 This invention relates to unsaturated derivathyl, dipropyl-naphthyl, benzyl, naphthyl-butyl, tives of 3-sulfolano1 and more particularly to phenethyl, vinyl-phenyl, crotonyl-naphthyl, resinous polymers thereof. methallyl-phenyl, triallyl-naphthyl, naphthyl- The potential value of sulfur in plwtic mateallyl, 2-phenyl-ethenyi, phenyl vinyl carbinyl, rials has been recognized since the discovery that cinnamyl, acetyl, propionyl, caproyl, stearacyl, it makes possible the vulcanization of rubber. benzoyl, cyclopentyl, :ethyl-cyclohexyl, tributyl- There have been developed a number of sulfurcyclohexyl, cyclopentenyl, cyclohexenyl, vinyl containing plastics, notably the olefin-sulfur dicyclohexenyl, thioenyl, furyl, loutyl carbothionyl, oxide resins, urea-thioformaldehyde and the suloctyl carbothionyl, decyl carbothionyl, etc.

fonamide resins. Each of these has properties For the purposes of the invention the most peculiar to itself which make it successful in a desirable unsaturated radicals (R1) are those particular field. However, the uses of sulfurwhich have an unsaturated linkage'of aliphatic containing resins are limited and there has been character between two carbon atoms, one of apparent for some time the need of combining which is joined to a saturated carbon atom from selected properties of the sulfur resins with so. which stems, a free valence of the radi al. Of lected properties of ethenoid resins. these a preferred group consists of allyl-type An object of the present invention is the proradicals, which are monovalent radicals having duction of new resins. A further object is the an ol fini do ble bo d between two arbon production of modified sulfur-containing resins. m n o which s J d to a saturated A furth r bj ct i th rodu tion f re in from bon atom from which stems the free valence of ulfur-gontainjng monomers modified b th the radical. Allyl-type radicals have the structure presence in the molecule of an ethylenically unan a, a,

saturated carbon-to-carbon bond. A still further i object is the production of resins having certain I properties due to the presence of sulfur and other 5 properties directly attributable to an ethenoid wherein each R is a substituent, such as hydroresin structure. Further objects will be apparent gen, halogen or an organic radical, preferably a from the description given hereinafter. hydrocarbon radical. In general, the most re- These objects are accomplished in accordance active allyl-type radicals have a terminal methwirth the invention by polymers of unsaturated 3o ylene group, i. a. they have the structure ethers and thioethers of 3-sulfolano1. The mono- R1 meric compounds have the structure represented A l by the general structural formula: CH3:

R: R: a RP wherein each R is substituent, such as hydrogen, halogen, or an organic radical. A preferred sub-group consists of those in which the free valence or the radical stems from a primary or v secondary carbon atom, as indicated by the struca so tural formula wherein X is O or S; R1 is an unsaturated radical l g and R2, Ra, R4, R5, R6, R7 and Rs are each hy- 03210 drogen, halogen orv an organic radical, such as wherein each R is as previously stated for allylan alkyl, alkenyl, alkynyl, aralkyl, aryl, acyl, type radicals. In the compounds of the present alicyclic, alicanbocyclic, or heterocyclic radical. invention, allyl-type radicals preferably have not Examples of organic radicals are methyl, ethyl more than about 18 carbon atoms and contain at propyl, isopropyl, normal butyl, isobutyl, seco dleast one unsaturated Carbowt b n linkage ary butyl, tertiary butyl, normal pentyl, isopentyl, for each 6 carbon atoms.

secondary pentyl, hexyl, normal octyl, iso-octyl, Examples of preferred allyl-type radicals are normal decyl, isodecyl, dodecyl, tetradecyl, cetyl, v1, ethyl vinyl carbinyl, ethyl vinyl carbinyl, stearyl, and trimethyl octodecyl, allyl, methallyl, propyl vinyl carb y Inethallyl, yl, chlorocrotyl, methyl vinyl carbinyl, butenyl, pentenyl, allyl, propallyl, methyl isopropenyl carbinyl, ethyl hexenyl, propargyl, geranyl, oleyl, phenyl, naphisopropenyl carbinyl, and 2-ethyl propene-2-yl-1 thyl, anthryl, tolyl, xylyl, secondary butyl-naphhexene-1yne5-y1-3, pentadiene 'ifi-yl-l'i, 2"

aerator methyl pentene-l-yne=yl-3, and 2,5-dimethyl hexadiene-li -yl -i. Other allyl-type radicals are dimethyl vhiyi carbinyl, methyl ethyl vinyl carhinyl, diethyl vinyl carbinyl, dimethyl isopropenyl carbinyl, methyl ethyl isopropenyl carblnyl, diethyl isopropenyl oarbinyl, 2-ethyl-3-methylhutenel-yl-3, crotyl, methyl propenyl canbinyl, ethyl propenyl carbinyl, dimethyl propenyl car. binyl, i-methyl==2-methyl-=butene-2-yl-l, l-eithyl- 2-methyl-butene 2-yl-i, isobutenyl earbinyl, cyc1ohexene2-yl cyclopentene-=2-yl=l, cinnamyl, hexadiene=2, -yl= hexadiene-2,5-yl-l, butadiene-2,8-yl1, hexadieneQj-yk-Z, 8,7-dimethyl octadiene-l'Z-yl-l, etc.

As to the compounds of the invention a preferred subgroup consists of those in accordance with the first general structural formula given hereinabove wherein R1 is an allyl-type radical, X is and R2, R3, Re Re, Re, R: and Rs are each an open-chain aliphatic hydrocarbon radical of from 1 to about carbon atoms, examples of which radicals are methyl, ethyl, propyl, iso propyi, normal butyl, isobutyl, secondary butyl, tertiary butyl, normal pentyl, isopentyl and secondary pentyl. Representative examples of specific compounds are allyl 3-sulfolanyl ether, methallyl 3-sulfolanyl ether, chloroallyl 3-sulfolanyl ether, crotyl 3-sulfolanyl ether, methylvinylcarbinyl 3-sulfolanyl ether, allyl l-methyl- 3-sulfolanyl ether, etc.

3-sulicianol is otherwise named 3-hydroxythiolene-l, i-diozrlde and 3-hydroxy cyclotetramethylene sulfone. It can be prepared by the addition of water to 3-sulfolene (which is 3- thiolene-i, i l-dioxide or beta-butadiene sulione) or to z-sulfolene (which is 2-thiolene-l, l-dioxide or alpha-butadiene sulfone) in the presence of a strong base. The unsaturated ethers of 3-sul- :Eolanol can be prepared by the addition of the corresponding unsaturated alcohol to 3=-suliolene or to 2-suliolene in the presence of a strong hase. preparation of the unsaturated ethers is described in the co-pendirig application of Morris Shokal, Serial. 4%,130, filed June 6, 1942. The thioethers can be prepared in a correspond ing manner. The preparation of the sulfolenes is described in British Patent 361,341, German Patent 236,386, German Patent 506,839 and by Backer and Strating in Rec. trav. chim. 53, 525-5e3 (1934).

The compounds can be polymerized singly or in admixture with one another or with other polymerizaole compounds. Among such other compounds are mono-ethylenic compounds, which contain a single polymerizable carbon-to-carbon double bond, of which an important subclass consists of those comp n-ds containing in the molecule a terminal me lene group attached to carbon by ethyl-e ic double bond CH2=C EX= am les this subclass of compounds are styrene, methyl many vinyl and allyl deand the nitriles and many of the esters c alpha suostituted acrylic acids.

group of cc=polymerizable compounds consists those compounds having two or more conjugated carloon=to-carbon double bonds, such as butadiene and substituted butadiene, as well as polymers of acetylene, such as vinyl and dl vinyl acetylene. Others are unsaturated cyclic compounds such as coumarone, indenc, furfural and cyclohexene.

Some or the most important co-polymerizable compounds, however, have two or more polyme izsable non-conjugated double bonds. Here an important subclass consists of the unsaturated aliphatic poly-esters of saturated polybasic acids, examples of which are divinyl, diallyl, and dimethallyl esters of oxalic, malonic, citric and tartartic acids, and the corresponding tri-esters of citric acid. Another subclass consists of the unsaturated aliphatic polyethers of saturated polyhydric alcohols, such as divinyl, diallyl and dimethallyl ethers of glycol, di-ethylene glycol,

tri-ethylene glycol, trimethylen glycol, propylene glycol, the corresponding diand tri-ethers of glycerol, and similar derivatives of diglycerol, triglycerol, mannitol, sorbitol, pentaerythritol and the like involving two or more hydroxyl groups of the polyhydric alcohol. Another subclass consists of the unsaturated aliphatic organic acid poly-esters of polyhydric alcohols, such as the acrylic and methacrylic polyesters of glycol, diethylene glycol, propylene glycol, trimethylene glycol, ethylidene glycol, glycerol, diglycerol, manmtol, sorbitol and resorcinol. merizable unsaturated compounds containing two or more unsaturated carbon-to-carbon linkages unconjugated with respect to one another are the unsaturated aliphatic alcohol esters of the unsaturated aliphatic acids. Examples cf these compounds are the vinyl, allyl, and methallyl esters of acrylic, methacrylic, chloro-acrylic, crotonic, itaconic, citraconic and cinnamic acids. Another class consists of the unsaturated polyesters of dibasic aromatic acids, such as divinyl, diallyl and dimethallyl esters of phthalic acid, isophthalic acid, terephthalic acid and the naphthalene dicarboxylic acids. Instead of the esters and ethers, the corresponding sulfur and nitrogen compounds, i. e. thio-esters, thio-ethers, amides and amines, may be used. The most important polymerizable compounds of the group having two or more polymerizable non-conjugated double bonds are, however, those containing oxygen.

The monomers of the invention may be polymerized also in the presence of already-formed plastics, including natural resins, cellulose derivatives and synthetic resins. Other modifiers, including plasticizers, stabilizers, lubricants, dyes, pigments and fillers, may be added to the monomer prior to polymerization or to partially polymerized material during polymerization, provided they do not chemically react with or otherwise adversely affect the ingredients of the reaction mixture. Otherwise, these modifiers may be added following polymerization. The nature and amount of the modifiers used will depend upon the particular material involved, upon the method. of preparation and upon the intended use of the product.

The polymerization of the monomer is usually effected according to" known procedures. The compounds can be polymerized in bulk in the absence of solvent or diluent to form ternary resins. Polymerization can be effected in solution in a substance which is a solvent for the monomer and polymer, or which is a, solvent for the monomer but a non-solvent for the polymer. A useful modification of this procedure is polymerization in solution in a substance which is a hot-acting solvent for the polymer. Molding power is conveniently formed by polymerization in dispersion in a non-solvent; in which case the dispersion may be a true emulsion or, more preferably, an impermanent suspension. Emulsifying, granulating and wetting agents may be present. It is also possible to effect polymerization by atomizing monomer or a solution thereof in the form of a fine spray into a heated chamber containing an inert gas. In all such cases the Other polyaaraeer polymerization may be either continuous or discontinuous and may be conducted at atmospheric, superatmospheric or reduced pressure. It is likewise feasible to polymerize monomer dispersed in the interstices in the fibrous material such as a fabric. Further, it may be sometimes desirable to polymerize the monomer in the form of a thin sheet which may be subsequently stripped from the surface to which it has been applied or which may be left on the surface in the form of a coating.

Polymerization is usually energized by heat, although both heat and light can be used. Temperatures of about 60 C. to about 150 C. are preferred. Catalysts can be used to hasten polymerization. The common peroxide types of cat-= alysts such as benzoyl peroxide, acetyl peroxide, benzoyl acetyl peroxide, lauryl peroxide and hydrogen peroxide are preferred. Oxygen and ozone markedly afiect the rate of polymerization. In most cases persulfates can be used as catalysts. Polymerization of the monomer is retarded by polymerization inhibitors, such as, for example, hydroquinone and other diand tri-hydroxy aromatic compounds. Inhibitors may be used to completely, or substantially, completely, prevent the polymerization of monomeric material in storage or may be present in the material during polymerization,'usually in the concurrent presence of a polymerization catalyst, for the purpose of controlling the rate thereof or of producing a product of certain desired properties.

The compounds will usually be substantially completely polymerized, in which case they may have a molecular weight of more than about 2,000. The material can, however, if desired, be only partially polymerized, yielding a syrup which can usually be subsequently subjected to more complete polymerization. An important process consists in the partial polymerization of the material in one vessel followed by the transfer of the ma terial to another vessel (a mold) where the polymerization is completed. Syrup or monomer can be mixed with preformed polymer of the same or a difierent substance, forming a pourable mixture or a dough which is then solidified in a required shape by subjecting the mass in a. mold to polymerization conditions, usually with the application of heat and pressure. Fibrous material, such as paper or cloth may be impregnated with monomer or syrup, followed by completion of the polymerization.

The products of the invention are thus normally liquid to solid, preferably solid, resinous polymers of selected derivatives of 3-sulfolanol and substituted 3-sulfolanol. They are usually substantially colorless and odorless. They can be produced in completely transparent form. Notable among the characteristics of the preferred compounds is their inherent flexibility which renders them suitable for many exacting uses with out the addition of a plasticizer. This is especially important where polymers must be kept flexible while immersed in a liquid of such character that otherwise the selection of a proper plasticizer would involve a compromise between the desired plasticity characteristics of the polymer and the solubility characteristics of the plasticizer. They are resistant to weather and to the action of many solvent and swelling agents.

The solid resinous polymers can be produced as sheets, rods, tubes and filaments. They make desirable ternary resins. They can be castv in an infinite variety of shapes. They can be subjected to extrusion and to injection and compression molding in the presence or absence of added dilu ents. Laminated structures, particularly laminated paper structures, containing the polymers display-remarkable flexibility. some of the poly= mers form tough adherent flexible coatings. They may be used as electrical insulation. Fibrous sheet material impregnated with the polymers has the proper degree of stifiness for many applica tions. In sheets, alone or, preferably, supported upon an open-mesh framework, the material may be used as a glass substitute.

The following examples are given for the purpose of illustrating the invention and are not to be considered limiting. Parts are on a weight basis.

Example I A mixture of 25 parts of allyl 3-sulfolanyl ether, parts of diallyl phthalate and 5 parts of benzoyl peroxide was held at 70 C. in an open vessel. The resulting polymer was a hard, infusible, slightly yellow resin.

Eramplc Iii" 100 parts of methallyl 3-sulfolanyl ether polymerized in the presence of 5 parts of benzoyl per= oxide on heating at 55 C. for 290 hours. The liquid polymer could be used as a. baking enamel.

Example IV A mixture of allyl i-l sulfolanyl ether, 10 parts, and diallyl phthalate, parts, gelled in. less than 16 hours when held at in. the presence of about 5 parts of be; peroxide. The com-- pletely polymerized r l was solid resin having a light straw .d ldarcol hardness of 35-36.

Example V 30 parts of methallyl 3-suliolanyl ether was polymerized with 255 s r diallyl phthalate with about i i parts of e oxide at 65 C. The resiuting strawwo ores had a Barcol hardness of Gulvrn.

A car-polymer or" the B Sulfolanyl ether of the a,adial1yl ether of glycerol with diallyl phthalate, in the ratio 10:85, produced by heating at 85 C. in the presence of 5% benzoyl peroxide, had a light straw color and a Barcol hardness of 36.

Example VII Nonenyl 3-sulfolanyl ether, 10 parts, and diallyl phthalate, 85 parts, were heated in admixture with 5% of benzcyl peroxide at 65 C. for hours. The solid resin had a Barcol hard ness 17.

Example Vii! resin of light color was produced by c0- polymerizing S-sulfolanyl (methallyl carbinyl) ether, 10 parts, with diallyl phthalate, 85 parts, in the presence of 5% of benzoyl peroxide. The resin had a Barcol hardness of 38-39.

We claim as our invention:

1. resin comprising a polymer of aeraem 3-sulfo1anyl ether, which ether has the structural formula:

A polymer of an ether of 3-sulfolanol, which other has the structural formula:

wherein R is an a1ken-2-y1 radical of 3 to 18 carbon atoms.

5. A polymer of allyl 3-sulfolany1 ether, which ether has the structural formula:

6. A polymer of methallyl 3-sulfolanyl ether, which ether has the structural formula:

I CH| I on; -CH3OCH-CH1 H3 Hz EDWARD C. SHOKAL. RUPERT C. MORRIS.

REFERENCES CITED 25 The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Delfs Oct. 22, 1940 OTHER REFERENCES Schrlner and Fuson, Identification of Organic Compounds pub. by Wiley, N. Y., 1940, pages 41 Number 35 and 43. 

